Single phase carbonylation of aromatic halides to carboxylic acid salts

Abstract

A process for preparing carboxylic acid salts by the reaction of carbon monoxide with substituted or unsubstituted aromatic halides or an aliphatic organic halide. The process comprises the catalytic single phase carbonylation of the halide utilizing in addition to carbon monoxide, a palladium catalyst, an excess of tertiary phosphine, optionally an amine compound, with an alkali metal or alkaline earth metal base added during the reaction to form the salt.

What is claimed is: 
     
       1. A process for preparing carboxylic acid salts comprising the single phase carbonylation of at least one organic halide in the presence of an alcohol, CO, and a base in conjunction with a palladium catalyst and an excess of tertiary phosphine, and wherein the base and excess phosphine is added during the reaction at a rate necessary to prevent side-product formation and catalyst decay. 
     
     
       2. The process of claim 1 further comprising the use of a hindered amine compound. 
     
     
       3. The process of claim 2 wherein the amine compound is a tertiary hindered amine base of the formula R' 3  N, wherein R' comprises C 3  -C 10  branched aliphatic compounds, cyclic compounds and aromatic compounds or mixtures of the above. 
     
     
       4. The process of claim 3 wherein the tertiary hindered amine base is N,N-diisopropylethyl amine. 
     
     
       5. The process of claim 3 wherein the tertiary hindered amine base is N,N-diisopropylmethyl amine. 
     
     
       6. The process of claim 3 wherein the tertiary hindered amine base is dicyclohexyl ethyl amine. 
     
     
       7. The process of claim 1 wherein the base is an alkali metal hydroxide or oxide. 
     
     
       8. The process of claim 7 wherein the base is potassium hydroxide. 
     
     
       9. The process of claim 1 wherein the base is an alkaline earth hydroxide or oxide. 
     
     
       10. The process of claim 1 wherein the excess tertiary phosphine is added in the form of triphenyl phosphine. 
     
     
       11. The process of claim 1 wherein the catalyst is a palladium II complex having the formula PdX 2  L 2 , where X is a halide and L is a tertiary phosphine. 
     
     
       12. The process of claim 11 wherein the palladium catalyst is PdCl 2  (PPh 3 ) 2 . 
     
     
       13. The process of claim 11 wherein L is a benzonitrile. 
     
     
       14. The process of claim 1 wherein the halocarbon is benzyl chloride. 
     
     
       15. The process of claim 13 wherein the benzonitrile reacts with phosphine in situ. 
     
     
       16. The process of claim 1 wherein the alcohol is isopropanol. 
     
     
       17. The process of claim 1 wherein the alcohol is methanol. 
     
     
       18. The process of claim 1 conducted under anhydrous conditions. 
     
     
       19. The process of claim 1 wherein the excess phosphine to palladium ratio is above about 2:1 to 100:1. 
     
     
       20. The process of claim 15 wherein the excess phosphine to palladium ratio is from about 3:1 to 30:1. 
     
     
       21. The process of claim 16 wherein the excess phosphine to palladium ratio is from about 5:1 to 15:1. 
     
     
       22. The process of claim 1 wherein the base is used in a molar ratio of from about 1 to about 4 per mole of the halocarbon. 
     
     
       23. The process of claim 22 wherein the base is used in a molar ratio of from about 2 to about 3 mole per mole of the halocarbon. 
     
     
       24. The process of claim 1 wherein the base and phosphine is added at a rate sufficient to prevent precipitation of the catalyst. 
     
     
       25. The process of claim 1 wherein the base is added at a rate sufficient to prevent formation of by-product ethers. 
     
     
       26. The process of claim 1 wherein the organic halide is benzyl chloride. 
     
     
       27. The process of claim 1 wherein the reaction is conducted at from atmospheric pressure to pressures of about 351.54 Kg/cm. 
     
     
       28. The process of claim 1 wherein the reaction is conducted at temperatures of from about 0° C. to about 150° C. 
     
     
       29. The process of claim 28 wherein the reaction is conducted at temperatures of from about 50° C. to about 100° C.